Benzothiazole azo 2,3-hydroxynaphthoic acid amide dyes



United States Patent 3,ll99,653 BENZOTHIAZGLE AZQ 2,3-HYDRXY- NAPHTHQECAll AMEDE EYES James M. iltraley and Raymond C- Harris, Kingsport,

Tenn, assignors to Eastman Kodak Company, Rochester, N.Y., a corporationof New dersey N0 Drawing. Filed Jan. 21, 196d, Ser. No. 3,723 Claims,(Cl. 2ee 1ss T [his invention relates to new azo compounds and theirapplication to the art of dyeing or coloring. More particularly, itrelates to certain metallized and nonmetallized benzothiazole azocompounds and their application to the dyeing or coloring ofacrylonitrile polymeric materials, especially polyacrylonitrile textilematerials.

The azo compounds of our invention consist of the mono-azo compounds,devoid of a water-so-lubilizing group, having the formula:

wherein Ar represents an ortho-arylene radical of the benzene series, Rrepresents an alkylene radical having 2 to 3 carbon atoms, R representsan alkyl radical having 1 to 4 carbon atoms and wherein N(R)collectively represents a member selected from the group consisting of amorpholinyl radical and a piperidyl radical and their metal complexescontaining a metal selected from the group consisting of nickel, cobaltand chromium.

The non-metallized monoazo compounds: of our invention are prepared bydiazotizing a Z-aminobenzothiazole compound having the formula:

wherein Ar represents an or-tho-arylene radical of the benzene seriesdevoid of a water-solubilizing group and coupling the diazoninm compoundobtained with a naphthalene compound having the formula:

wherein R, R and N(R') have the meaning previously assigned to them. Themetallized azo compounds of our invention are prepared by metallizingthe non-metallized azo compounds with appropirate metallizing agents inaccordance with known metallizing procedures. The manner in whichmetallization can be carried out is fully described hereinafter.

Nickel chloride, nickel bromide, nickel sulfate, nickel acetate, nickelformate, nickel thiocyanate [Ni(SCN) cobaltous bromide, cobalticchloride, cobaltous chloride, cobaltous acetate, cobalt thiocyanate[Co(SCN) chromium trichloride, chromium tribromide, chromic sulfate,chromic acetate and chromium thiocyanate [Cr(SCN) for example, areillustrative of the metallizing agents that can be employed.

Both the non-metallized and the metallized azo compounds of ourinvention can be applied to polyacrylonitrile textile materials in theform of an aqueous dispersion. Coloration can also be effected byincorporating the non-metallized or metallized azo compounds into thespinning dope, spinning the fiber as usual and converting the 3,099,553Patented July 39, 1963 non-metallized azo compounds to their metallizedform if desired. Also the metallizing agent can be incorporated in thespinning dope, the fiber spun as usual and then treated in a dyebathcontaining one or more of the nonrnetallized azo compounds to form themetal complex on the fiber.

The non-metallized monoazo compounds yield orange to red shades onpoly-acrylonitrile materials. The metallized compounds yield violet toblue shades, which have good fastness to light, washing and gas, onpolyacrylonitrile materials, such as acrylic fibers. The metallizeddyeings have better fastness to washing than the corre spondingnon-metallized dyeings and frequently have improved tastness to light.Among the acrylonitrile polywere that can be dyed or colored with thenonrnetallized and metallized azo compounds of our invention are thosedisclosed in Straley and Giles U.S. Patent 2,857,372, issued October 21,1958.

2-aminobenzothiazole, 2-amino-6-methylsul-fonylbenzothiazole,Z-amino-6-ethylsul fonylbenzothiazole,2-amino-6-n-propylsulfonylbenzothiazole,2-amino-G-n-butylsulfonylbenzothiazole, 2-arnin'obenzothiazole-6-N-methylsulfionamide,Z-aminobenzothiazole-6-N-ethylsulfonamide,Z-a-minobenzothiazole-o-N-n-propylsulfonamide,2-aminobenzothiazole-6-N-n-butylsulfonamide,Z-amino-6-rnethoxybenzothiazole, 2-amino-6-ethoxybenzothiazole,Z-amino-6-n-propoxybenzothiazole, Z-amino-6-n-butoxybenzothiazole,2-amino-6-methylbenzothiazole, Z-amino-6-ethylbenzothiazole,2-amino-6-n-propylbenzothiazole, Z-amino-6-n-butylbenzothiazole,Z-amino-o-p-hydroxyethylbenzothiazole,Z-amino-6-y-l1ydroxypropylbenzothiazole,2-amino-6-6-hydroxybutylbenzothiazole,2-amino-6-acetylaminobenzothiazole,2-arnino-6-n-propionylaminobenzothiazole,Z-amin0-6-n-butyrylarninobenzothiazole,Z-amino-6-thiomethylbenzothiazole, 2-amino-6-thiocyanobenzothiazole,2-amino-6-tri-fluoromethylbenzothiazole, 2-amino-6-chlorobenzothiazole,2-amino-6-nitrobenzothiazole, 2-amino-4,7=dimethoxybenzothiazole,Z-amino-S,6-dimethoxybenzothiazole, 2-amino-4,7-diethoxybenzothiazole,and 2-arnino l,6-di-methylbenzothiazole are representative of theZ-aminobenzothiazole compounds used in the preparation or" the azocompounds of our invention.

2-hydroXy-N-3 (B-dimethylaminoethyl naphthamide, 2-hydr0xy-N-3-(fi-diethylaminoethyl) naphthamide, 2-hydroxy-N-3l8-di-n-propylaminoethyl) naphthamide, 2-hydroxy-N-3 fi-di-n-butylaminoethyl) naphth amide, 2-hydroxy-N-3 ('y-dimethylaminopropyl) naphthamide,2-hydroxy-N-3- y-diethylaminopropyl naphthamide, 2 hydroxy-N-3-di-n-butylarninopropyl) naphthamide, 2-hydroxy-N-3 B-morpholinylethylnaphthamide, Z-hydroXy-N-B 'y-morpholinylpropyl) naphthamide,2-hydroxy-N-3 p-piperidylethyl naphthamide and Z-hydroxy-N-S piperidylp-ropyl) naphthamide are illustrative of the coupling componentsused in preparing the 2.20 compounds of our invention.

The coupling components can be prepared by reacting 32-hydroxy-3-naphthoic acid chloride or 2-acetoxy-3-naphthoic acidchloride with an amine having the formula:

wherein R, R and N(R) have the meaning previously assigned to them. When2-acetoxy-3-naphthoic acid chloride is employed the acetyl group issplit off by known methods after the reaction with the amine iscomplete. The following examples illustrate the invention.

Example 1 15 grams of Z-aminobenzothiazole were dissolved in 240 cc. ofwater and 140 cc. of 96% sulfuric acid, cooled to C., and diazotized bythe addition of a nitrosyl sulfuric acid solution previously preparedfrom 7.2 grams of sodium nitrite and 50 cc. of 96% sulfuric acid.Diazotization was carried out at a temperature below C., with stirring.A coupling solution was prepared by dissolving 27 grams of.2-hydroxy-N-3-(y-dimethylaminopropyl)naphthamide in 400 cc. of waterand cc. of glacial acetic acid and the temperature was brought to 5 C.by the addition of crushed ice. The diazonium solution was added over aperiod of about minutes, with stirring, and stirring was continued for45 minutes longer, adding ice as necessary to maintain the temperatureof the reaction mixture at 5 C. or below. Upon completion of thecoupling reaction the reaction mixture was made neutral to Congo redpaper by the addition of sodium carbonate and the dye compound whichprecipitated was recovered by filtration, Washed well with water andair-dried. The dye compound thus obtained has the formula:

CH3 H (EONOHzCHzCHzN and dyes polyacrylonitrile fibers red shades. Thenickel, cobalt and chromium complexes yield blue shades on acrylicfibers such as Orlon 42 and Verel which are fast to light, washing andgas.

Example 2 1.08 grams of the non-metallized monazo dye compound ofExample 1, 15 cc. of acetone and 2 cc. of 28% aqueous ammonium hydroxidewere refluxed together and a solution of 0.7 gram of Ni(OOCCH -4H O in15 cc. of 50% aqueous acetone was added over a period of 15 minutes.Refluxing was continued for three hours after which the reaction mixturewas poured into 400 cc. of water and the temperature brought to 80 C. 10grams of sodium chloride were added, with stirring, and then thereaction mixture was allowed to cool to room temperature. The metallizeddye product, a so-called 1:2 complex in which nickel and the monoazocompound are combined in the ratio of about one atom of nickel to 2molecules of the monoazo compound, which precipitated was recovered byfiltration, washed with a 2% aqueous sodium chloride solution andair-dried. lt colors polyacrylonitrile textile fibers, such as Orlon 42and Verel, blue shades which have good fastness to light, washing andgas.

Example 3 A solution of nitrosyl sulfuric acid was prepared from 1.52grams of sodium nitrite and 20 cc. of 96% sulfuric acid. 20 cc. ofpropionic-acetic (1:5 acid were added below 8 C. and then a solution of3.6 grams of 2-ami-no- 6-methoxybenzothiazole in 20 cc. ofpropionic-acetic (1:5) acid was added at a temperature below 5 C. Thereaction mixture thus obtained was stirred at 5 C. for two hours. Thediazonium solution thus prepared was stirred into a coupler solutionprepared by dissolving naphthamide in 100 cc. of 5% aqueous acetic acidand enough crushed ice was added to maintain the temperature below 5 C.After stirring for an additional two hours, the reaction mixture wasmade neutral to Congo red paper by the addition of sodium carbonate andthe dye compound which precipitated was recovered by filtration, washedwell with water and dried. It dyes polyacrylonitrile orange shades. Thenickel, cobalt and chromium complexes yield slightly greener shades onacrylic fibers, such as Orlon 42 and Verel, which are :fast to light,gas and washing.

Example 4 23 grams of 2-arnino-6-methylsulfonylbenzothiazole werediazotized and the diazonium compound obtained was coupled with 28 gramsof 2-hydroxy-N-3-(fl-diethylaminoethyl)naphthamide. Diazotization,coupling and recovery of the dye compound formed were carried out inaccordance with the procedure described in Example 1. The dye compoundobtained dyes polyacrylonitrile textile materials orange shades. Thenickel, cobalt and chromium complexes yield blue-violet shades onacrylic fibers such as Orlon 42 and Verel which are fast to light,washing and gas.

- Example 5 3.3 grams of 2-amino--methylbenzothiazole were diazotizedand the diazonium compound obtained was coupled with 5.3 grams of2-hydroxy-N-3-(fi-dimethylaminoethyhuaphthamide. Diazotization, couplingand recovery of the dye compound formed were carried out in accordance\m'th the procedure described in Example 3. The dye compound obtaineddyes polyacrylonitrile textile materials red shades. The nickel, cobaltand chrornium complexes yield blue shades on acrylic fibers, such asVerel and Orion 42, which are fast to light, washing and gas.

Example6 15 grams of '2-aminobenzothiazole were diazotized and thediazon-ium compound obtained was coupled with 28 grams of2-hydroxy-N-3-(fl-diethylaminoethyl)naphthamide. Diazotization, couplingand recovery of the dye compound formed were carried out in accordancewith the procedure described in Example 1. The dye compound obtaineddyes polyacrylonitrile textile materials red shades. The nickel, cobaltand chromium complexes yield blue shades on acrylic fibers, such asVerel and Orlon 42, which are fast to light, washing and gas.

Example 7 15 grams of Z-aminobenzothiazole were diazotized and thediazonium compound obtained was coupled with 25.5 grams of 2hydroxy-N-3-(B dimethylaminoethyl)naphthamide. Diazotization, couplingand recovery of the dye compound formed were carried out in accordancewit-hthe procedure described in Example )1. The dye compound obtaineddyes polyacrylonitrile textile materials red shades. The nickel, cobaltand chromium complexes yield blue shades on acrylic fibers, such asVerel and Orlon 42, which are fast to light, washing and gas.

Example 8 4.21 grams of the non-metallized dye of Example 1 were addedin small portions to a solution of 5.4 grams of CrCl -6H O in 50 cc. ofethyleneglycol at 140 C. The reaction mixture was stirred at 140 C. forone hour longer, cooled to C. and then poured into cc. of a 10% aqueoussodium chloride solution. Impurities were removed by filtration and thedye product was precipitated from the filtrate by making it basic with10% NHQOH- The chromium complex, a so-called 1:2 complex in whichchromium and the monoazo compound are combined in the ratio of about oneatom of chromium to 2 molecules of the monoazo compound, of the dye ofExample 1 was recovered by filtration, washed with a aqueous sodiumchloride solution and air-dried. It yields reddish-blue shades onpolyacrylonitrile textile materials made of Verel or Orlon 42 acrylicfibers which have good fastness to light, gas and washing.

Example 9 188 grams of Z-hydroxy 3 naphthoio acid were slurn'ed in 1000cc. of dry benzene. A solution of 122 grams of SoCl in 500 cc. of drybenzene was added over a period of 30 to 45 minutes. The reactionmixture resulting was stirred for 2.5 hours at room temperature, thenraised slowly to 60 C. and held at this temperature until a clearsolution resulted (about 2 hours). The excess SOCI S0 and HCl wasremoved under vacuum while keeping the pot temperature at 60 C. orbelow. The last traces of $00,, S0 and HCl were removed by passing aslow stream of dry air through the reaction mixture for about minutes.The reaction mixture was cooled to 25 C. and 138 grams of anhydrous K COwere added, after which a solution of 110 grams of3-dimethylaminopropylamine in 300 cc. of dry benzene was added dropwisewhile keeping the pot temperature at 60 C. or below. The reactionmixture was stirred 6 hours longer at room temperature, then raised to65 C. and filtered hot. The material collected on the filter was washedwith three 2-liter portions of hot benzene. The combined filtrates wereconcentrated under vacuum to /3 their volume below 70 C. The reactionmixture was cooled to room temperature. The desired product whichprecipitated was recovered by filtration. A yield of 240 grams ofN-('y-dimethylaminopropyl) 2 hydroxy-3- naphthamide was obtained.

Following the general procedure described in the example just given theother naphthamide coupling components are readily prepared.

The following tabulation further illustrates the azo compounds of ourinvention and sets forth (1) the colors the non-metallized azo compoundsyield on polyacrylonitrile textile fabrics made of Verel or Orlon 4 2acrylic fiber and (2) the colors obtained when the non-metallizeddyeings are metallized with nickel thiocyanate. Original refers to thenon-metallized dyeing and Final refers to the metallized dyeing.

The non-metallized azo compounds disclosed in the foregoing tabulationcan also be metallized with a suitable cobalt or chromium metallizingagent, especially cobalt thiocyanate and chromium thiocyanate, to formthe cobalt and chromium complexes thereof. The cobalt complexes yieldabout the same colors as the corresponding nickel complexes. In the caseof the chromium complexes the color tends to be redder. As shownhereinbefore metallization can also be effected off the fiber.

The non-metallized and metallized azo compounds described herein can beapplied to acrylonitrile polymers, such as polyacrylonitrile andacrylonitrile graft polymers, in the form of an aqueous dispersion.

The following example illustrates one satisfactory Way in which thenon-metallized azo compounds can be used to dye an acrylonitrile polymertextile material. .1 gram of dye is dissolved by warming in 5 cc. ofmethyl Cellosolve. A 2% aqueous solutionof a nonionic surfactant, suchas Igepal CA (a polymerized ethylene oxide-alkylphenol condensationproduct), is added slowly until a fine emulsion is obtained and then thedye mixture is brought to a volume of 200 cc. with warm water. 5 cc. ofa 5% aqueous solution of formic acid or ace-tic acid are added and then10 grams of fabric made from an acrylic fiber is entered and in the caseof Orlon 42 the dyeing is carried out at the boil for one hour. In thecase of materials made of Verel acrylic fiber the dyebath temperatureshould not exceed C. in order to avoid damage to the fiber. The dyedmaterial is then washed well with water and dried. The metallizeddyeing, in which the 1:2 metal complex is formed in situ on the materialbeing dyed, can be obtained, for example, in accordance with theprocedure described in Example 10. A 3% solution of a salt, other thanthe thiocyanate salt, can be used. However, we have found the use of thethiocyanates of nickel, cobalt and chromium to be particularlyadvantageous.

The premetallized azo dyes can be applied in the same general manner asthe non-metallized azo dyes. However, in order to mitigate thepossibility of demetallization during dyeing 5 cc. of a 5% aqueoussolution of a weak acid such as boric acid is used instead of formicacid or acetic acid. Except for this change the dyeing conditions arethe same.

Example 10 A polyacrylonitrile textile fabric dyed red with a 1% dyeing(by Weight of pure dye) of the dye product of Example 1 was padded witha 3% aqueous solution of nickel thiocyanate under conditions such that a60 to pick up, based on the weight of the fabric, was obtained. Thepolyacrylonitrile fabric was then aged in a steam chest under 5 p.s.i.pressure for 10 minutes after which it was scoured at 60 C. with soapand water, rinsed well with water and dried. The polyacrylom'trilefabric was dyed a blue shade having good fastuess to light, washing andgas.

The non-metallized and metallized azo compounds described herein aredevoid of water-solubilizing groups such as the carboxylic acid and thesulfonic acid groups. Any other suitable method known to the art can beused to apply them to acrylonitrile polymeric materials.

The invention has been described in detail with particular reference topreferred embodiments thereof, but it will be understood that variationsand modifications can be effected within the spirit and scope of theinvention as described hereinabove and as defined in the appendedclaims.

The expression propionic-acetic (1:5) acid refers to a mixture ofpropionic and acetic acids in which there are five parts by volume ofacetic acid to 1 part by volume of propionic acid.

We claim:

1. The monoazo compounds, devoid of a watersolubilizing group, havingthe formula:

wherein X represents a member selected from the class consisting of ahydrogen atom, lower alkyl, lower alkoxy, nitro and thiocyano radicals,R represents an alkylene radical having 2 to 3 carbon atoms, Rrepresents an alkyl radical having 1 to 4 carbon atoms and wherein N(R)collecti-vely represents a member selected from the group consisting ofa morpholinyl radical and a piperidyl radical.

2. The monoazo compound having the formula:

.3. The monoazo compound having the formula:

4. The monoazo compound having the formula:

5. The monoazo compound having the formula:

CH3 H /S H10 0 ONCHzOHzCHzN CH3O- CH /O--N=N- N References Cited in thefile of this patent UNITED STATES PATENTS 2,128,256 Krzikalla et a1.Aug. 30, 1938 2,402,538 Dreyfus June 25, 1946 2,408,421 Grimmel et a1.Oct. 1, 1946 2,868,774 :Straley et a1. Jan. 13, 1959 2,916,482 Straleyet a1. Dec. 8, 1959

1. THE MONOAZO COMPOUNDS, DEVOID OF A WATERSOLUBILIZING GROUP, HAVINGTHE FORMULA: